Dyestuffs of pyrazolanthrone series and process of making same



Patented Sept. 20, 1932 UNITED STA E -OF E GEORG KALISGI-IER, or rnnnxronromrnn-manv," ummer: RIT'IER, or FRANK- ronT-oiv-THEmnm-rnonnivnnrn, HEINZ SCHEYEB'AND o'r'ro BAYER, or FRANK- ronr-oN 'rHE-Mirm, ennnalvxnssrelvons T0 GENERAL ANILINE' wonxs, me; or NEW YORK, NY; A CORPORATION OEDELAWABE r DYESTUFFS or PYRAZOLANTHRONE snnrns Ann rnocn ss or MAKING SAME No Drawing. Application filed July 15, '1930, Serial No; 468,198; and in Germany-'J'ulyw; 1929 This invention relatesjto new valuable fast vat dyestuffs for cotton and to a process for making same.

The new .dyestufls are obtained by; condensing a 2-carboxylic acid halide of pyrazolanthrone compounds with a cyclic ketone compound containing at least one freeamino gro'up which ketone is capableiof being'vatted"v and may be a dyestufl'. The acylated products thus obtained are valuable dyestuiis,

which can be transformed into soluble vats by means of an alkaline hydrosulfite' solution and which dyecottontherefrom fast shades varying according to the starting material used. It is a very surprising factin spite of the introduction of the high'molecular anthraquinone residues to which in 1- and 9-position aheterocyclic ring system is linked the condensation products formed yield easily soluble vats. I

As suitable amino-derivatives of cyclic ketone compounds capable-of being vatted a-monoand diamino-anthraquinones, amino-v anthrlmides and their carbaZohc der1vat1ves,

amino-anthanthrones, amino-pyranthrones, amino-dibenzanthrones, amino dibenzopyrenquinones. and their substitution products and derivatives, amino-thiazolanthrone-sultone and amino-.coeramidonines may be mentioned. "The condensation is carried out in a suitable'solvent suchias nitrobenzene or dichlorobenzene with or without the addition of an agent binding the hydrohalic acid formed by the reaction.

Pyrazolanthrone-Q-carboxylic acid chloride andits N -alkyL andYN-aralkyl-derivatires which are used as, starting materials for the production of dyestuffs. are easily obtainable by' the usual conversion of the corresponding carboXylic acids. 1'

Instead of starting from the N-alkylor I N aralkyl' derivatives of the" fpyrazolan thrOne-Q-carboxylic'"acid chloride the same result is obtained by converting the acylation 7 The same analogous productsare obtained by condensing l-halogen-anthraquinone carboxylic acid halides'with the aforesaid aminoderivatives of cyclic ketones and reacting with hydraz'ineonthe condensation products thus obtained. In a strikingmanner the ring closure to the pyrazolanthrone derivatives immediately occurswithout the formation of intermediates. Thev condensation with hydrazine-may beadvantageously carried out 7 by treating the components under pressure.

with the addition of a suitable solvent such as pyridine or in an aqueous suspension and using hydrazine hydrate or sulfate with the addition of the corresponding quantity of alkali. V

When using according to this latter modi-.

fication 15halogenranthraquinone-2-carboxylic acid halides for thecondensation with 'amino'compounds of the aforesaidkindthe I '7 same dyestuffs are obtained as by condensing pvrazolanthrone-2-carboXylic acid halides When starting from the isomeric: l-halo -v genanthraquinone l-carboxylic acid halides however the present process takes placein the same way and fast vat dyestuffs are also formed.

In order to further illustrate our invention the following examples are givenythe parts being by weight and all temperatures incentigrade. degreesybut it is tobe understood, that our invention is not limited to I the particular products nor reacting conditions mentionedtherein 7 Example 1 22 parts of" l-aminoanthraquinone are-l m xed with about 750 parts of nitrobenzene and 28 parts of pyrazolanthrone-Q-carboxylic acid chloride and the mixture is heated to boiling until no unchanged l-amino-anthraquinone can be detected. When cool the separated mass of crystals is filtered 0E and washed out with benzene. The new dyestufi thus obtained corresponds to the probable formula:

It forms yellow crystals and dyes cotton from a violet-reddish brown vat strong yellow shades of a good fastness. in concentrated sulfuric acid is orange colored. i

The same dyestuff is obtained in the following manner: 10 parts of'1-chloro-2-anthraquinone-carboxylic acid-a anthraquinone-amide of the formula:

are heated with 100 parts of anhydrous pyris dine in an apparatus provided with a reflux condenser and 3 parts of hydrazine hydrate are allowed to drop in. After boiling fora short time the formed dyestufi' is filtered off and is washed out with alcohol. It maybe purified, for instance by boiling with hypochlorite.

.The latter method of condensation may be I Example 12 parts of 1.5- or l-diamino-anthraquinone are heated with 28 partsof pyrazolanthrone-2-carboxylic acid chloride in the presence of nitrobenzene in the manner as de- 51 scribed in the first paragraph of Example 1..

The solution The dyestufls thus obtained correspond to the probable formulae:

respectively. They correspond in their properties with the dyestuff of Examplel and dye cotton yellow shades of a good fastness.

Ewample 3 25 parts of 1-amino-L-methoxy-anthraquinone are mixed with about 1000 parts of dichlorobenzene and 28 parts of pyrazolanthrone-2-carboxylic acid chloride and the mixture is heated to boiling in an apparatus provided with a reflux condenser until the,

evolution of hydrochloric acid has ceased. The dyestuff thus formed separates as orange-brown crystals. It corresponds probably to the formula:

o (ENE- It dyes cotton from a black-brown vat the same shade turning to a full orange when exposed to the air. The solution of the new dyestufi in concentrated sulfuric acid is dark red.

' Example 4 parts of 1-amino-4-benzoylamino-anthraquinone are mixed with about 1250 parts of nitrobenzene and 28 parts ,of pyrazolanthrone-2-carboxylic acid" chloride and 10 parts of anhydrous sodium. acetate and the a mixture is heated for hour to boiling in an apparatus provided with a reflux condenser. The reaction product separatinginthe form carboxylic of reddish brown crystals is filtered off and washed out with alcohol and water. The new dyestufi corresponds probably to the formula: V

It is soluble in concentrated sulfuric acid with an orange red color and dyes cotton from a brownish red vat full orange-brown shades of a good fastness.

The same dyestuif is obtained in the following manner: l-chloro-2-anthraquinone-' acid-1-benzoylamino-4c-anthraquinone-amide of the formula:

is condensed with hydrazine hydrate in a like manner as described in the second paragraph of Example 1. i

' Example 5 30 parts of N-methyl-pyrazolanthrone-2- carboxylic acid chloride are mixedwith about 1000 parts of dichlorobenzene and 23 parts of l-amino-anthraquinone and the mixture is heated to boiling in an apparatus provided s with a reflux condenser until the evolution of hydrochloric acid has ceased. The reaction product separating in form of yellowish brown crystals is filtered ofi and washed out. It corresponds probably totheformula:

NNOH:

The new dyestuff dyes cotton from a reddish brown vat yellow shades of a good fastness.

When replacing the 23 parts of l-aminoanthraquinoneby 25 parts of 1*amino-4- methoxy-anthraquinone or 3.3 parts of 1- amino-l-benzoy laminoranthraquinoneanalogous. dyestuffs are obtained dyeing cotton from a-black reddish brown vat full orange to orange-brown shades of a good fastness. fiw e f 1 10 partsi of the dyestufi described in paragraph 1. of Example l are mixed with 10 parts of toluene-sulfonio-acid-methylester, 8 parts of potassium carbonate and about 7 5'parts of nitrobenzene and the" mixture is heated to boiling for about 2 hours in an apparatus filtered o1f, washed out. It corresponds probably to the formula:

It dyes cotton from a red like claret violet shadesturning to a full'orange when exposed to the air andacidulated.

We claim act 1. A process for manufacturing new vat dyestuffs which process comprises condensing a pyrazolanthrone-Q-carboxylic acid halide of the formula:

. H O OC O-halogen r wherein X means hydrogen or an alkyl-group witha cyclic ketonecompound containing at least one free amino-group'and at least three 1 condensed benzene nuclei.

2. A process for manufacturing new vat dyestuffs which comprises condensing a pyrazol'anthrone-Q-carboxylic acid halide of the formula: a

wherein X means hydrogen or an alkyl-group with an aminoanthraquinone compound. I

3. As new compounds vat dyestuffs corresponding probably to the general formula L J; L 0

wherein X means hydrogen or an alkyl-group and n the number 1 0r 2.

4:. As new compounds the Vet dyestuffs corresponding probably to the general formula 1 INH' wherein Y means hydrogen or a methoxygroup.

5. As new compound the vat dyestufi' corresponding probably to the formula; 1

N--NH In testimony whereof, We affix our signatures.

GEORG KALISCHER. HEINRICH BITTER, HEINZ SCHEYER'.

OTTO BAYER. 

